A Two-phase Bromination Process Using Tetraalkylammonium Hydroxide for the Practical Synthesis of α-bromolactones from Lactones

Overview

Journal Beilstein J Org Chem

Specialty Chemistry

Date 2021 Dec 27

PMID 34956409

Authors

Yuki Yamamoto

Akihiro Tabuchi

Kazumi Hosono

Takanori Ochi

Kento Yamazaki

Shintaro Kodama

Akihiro Nomoto

Akiya Ogawa

Affiliations

Soon will be listed here.

Abstract

A simple and efficient method for α-brominating lactones that affords αbromolactones under mild conditions using tetraalkylammonium hydroxide (RNOH) as a base was developed. Lactones are ring-opened with Br and a substoichiometric amount of PBr, leading to good yields of the corresponding α-bromocarboxylic acids. Subsequent intramolecular cyclization over 1 h using a two-phase system (HO/CHCl) containing RNOH afforded α-bromo lactones in good yields. This method can be applied at the 10 mmol scale using simple operations. α-Bromo-δ-valerolactone, which is extremely reactive and difficult to isolate, could be isolated and stored in a freezer for about one week using the developed method. Optimizing the solvent for environmentally friendly large-scale syntheses revealed that methyl ethyl ketone (MEK) was as effective. In addition, in situ-generated α-bromo-δ-valerolactone was directly converted into a sulfur-substituted functional lactone without difficulty by reacting it with a sulfur nucleophile in one pot without isolation. This new bromination system is expected to facilitate the industrial use of α-bromolactones as important intermediates.

References

Studer A, Curran D . Catalysis of Radical Reactions: A Radical Chemistry Perspective. Angew Chem Int Ed Engl. 2015; 55(1):58-102. DOI: 10.1002/anie.201505090. View

Zhao B, Li Z, Wu Y, Wang Y, Qian J, Yuan Y . An Olefinic 1,2-Boryl-Migration Enabled by Radical Addition: Construction of gem-Bis(boryl)alkanes. Angew Chem Int Ed Engl. 2019; 58(28):9448-9452. DOI: 10.1002/anie.201903721. View

Petrone D, Ye J, Lautens M . Modern Transition-Metal-Catalyzed Carbon-Halogen Bond Formation. Chem Rev. 2016; 116(14):8003-104. DOI: 10.1021/acs.chemrev.6b00089. View

Saikia I, Borah A, Phukan P . Use of Bromine and Bromo-Organic Compounds in Organic Synthesis. Chem Rev. 2016; 116(12):6837-7042. DOI: 10.1021/acs.chemrev.5b00400. View

Zhao W, Lorenz N, Jung K, Sieber S . Fimbrolide Natural Products Disrupt Bioluminescence of Vibrio By Targeting Autoinducer Biosynthesis and Luciferase Activity. Angew Chem Int Ed Engl. 2015; 55(3):1187-91. DOI: 10.1002/anie.201508052. View

Panchal H, Clarke C, Bell C, Karad S, Lewis W, Lam H . Nickel-catalyzed, ligand-free, diastereoselective synthesis of 3-methyleneindan-1-ols. Chem Commun (Camb). 2018; 54(87):12389-12392. DOI: 10.1039/c8cc06388e. View

Baskar B, Dakas P, Kumar K . Natural product biosynthesis inspired concise and stereoselective synthesis of benzopyrones and related scaffolds. Org Lett. 2011; 13(8):1988-91. DOI: 10.1021/ol200389p. View

Chinchilla R, Najera C . The Sonogashira reaction: a booming methodology in synthetic organic chemistry. Chem Rev. 2007; 107(3):874-922. DOI: 10.1021/cr050992x. View

Tran Q, Wong W, Chai C . The identification of naturally occurring labdane diterpenoid calcaratarin D as a potential anti-inflammatory agent. Eur J Med Chem. 2019; 174:33-44. DOI: 10.1016/j.ejmech.2019.04.023. View

10.

Fang X, Wang P, Yi W, Chen W, Lou S, Liu G . Visible-Light-Mediated Oxidative Coupling of Vinylarenes with Bromocarboxylates Leading to γ-Ketoesters. J Org Chem. 2019; 84(23):15677-15684. DOI: 10.1021/acs.joc.9b02310. View

11.

Wu C, Brik A, Wang S, Chen Y, Wong C . Tetrabutylammonium fluoride-mediated rapid alkylation reaction in microtiter plates for the discovery of enzyme inhibitors in situ. Chembiochem. 2005; 6(12):2176-80. DOI: 10.1002/cbic.200500295. View

12.

Beletskaya I, Cheprakov A . The heck reaction as a sharpening stone of palladium catalysis. Chem Rev. 2001; 100(8):3009-66. DOI: 10.1021/cr9903048. View

13.

Surry D, Buchwald S . Dialkylbiaryl Phosphines in Pd-Catalyzed Amination: A User's Guide. Chem Sci. 2012; 2(1):27-50. PMC: 3306613. DOI: 10.1039/C0SC00331J. View

14.

Tan C, Yeung Y . Recent advances in stereoselective bromofunctionalization of alkenes using N-bromoamide reagents. Chem Commun (Camb). 2013; 49(73):7985-96. DOI: 10.1039/c3cc43950j. View

15.

Kambe N, Iwasaki T, Terao J . Pd-catalyzed cross-coupling reactions of alkyl halides. Chem Soc Rev. 2011; 40(10):4937-47. DOI: 10.1039/c1cs15129k. View

16.

Becker G, Wurm F . Functional biodegradable polymers via ring-opening polymerization of monomers without protective groups. Chem Soc Rev. 2018; 47(20):7739-7782. DOI: 10.1039/c8cs00531a. View

17.

Chen Z, Zhang X, Tu Y . Radical aryl migration reactions and synthetic applications. Chem Soc Rev. 2015; 44(15):5220-45. DOI: 10.1039/c4cs00467a. View

18.

Gu X, Yu N, Yang X, Zhu A, Xie J, Zhou Q . Enantioselective Hydrogenation of Racemic α-Arylamino Lactones to Chiral Amino Diols with Site-Specifically Modified Chiral Spiro Iridium Catalysts. Org Lett. 2019; 21(11):4111-4115. DOI: 10.1021/acs.orglett.9b01290. View

19.

Cholewczynski A, Williams P, Pierce J . Stereocontrolled Synthesis of (±)-Melokhanine E via an Intramolecular Formal [3 + 2] Cycloaddition. Org Lett. 2020; 22(2):714-717. PMC: 7662073. DOI: 10.1021/acs.orglett.9b04546. View

20.

Zhang X, Fevre M, Jones G, Waymouth R . Catalysis as an Enabling Science for Sustainable Polymers. Chem Rev. 2017; 118(2):839-885. DOI: 10.1021/acs.chemrev.7b00329. View